Dye preparations containing a metallized disazo dye and monopropanolamine

ABSTRACT

STABLE, CONCENTRATED DYE PREPARATIONS CONTAINING ONE METALLIZED DYE OF THE AZO OR AZOMETHINE SERIES AND MONOPROPANOLAMINE OR AN AMINOTHIOLE.

United States Patent Oflice 3,700,653 Patented Oct. 24, 1972 3,700 653DYE PREPARATIONS CONTAINING A METAL- LIZED DISAZO DYE AND MONOPROPANOL-15,207/ 67; Nov. 24, 1967, 16,573/ 67; Dec. 6, 1967, 17,060/ 67 Int. Cl.C09b 45/28 US. Cl. 260-148 15 Claims ABSTRACT OF THE DISCLOSURE Stable,concentrated dye preparations containing one metallized dye of the azoor azomethine series and monopropanolamine or an aminothiole.

This invention relates to stable, concentrated dye preparationscontaining one metallized dye of the azo or azomethine series andmonopropanolamine or an aminothiole. Highly suitable dye preparations ofthis type are liquid preparations of water soluble metallized dyescontaining, per 1 part by weight of dye, 2 to 15 or, preferably, 5 to 15parts by weight of water and 0.5 to 5 or, preferably, 0.5 to 2 parts byweight of monopropanolamine.

Dyes of the azo series, e.g. copper-containing disazo dyes, areespecially suitable for these preparations. It is desirable for them tobear the radical of a tetrazotized diaminodiphenyl, e.g. the radical ofa tetrazotised 4,4- diamino 3,3 dialkoxy-1,l-diphenyl, and as couplingcomponent a hydroxynaphthalenesulphonic acid, e.g. 2 moles of ahydroxynaphthalenesulphonic acid or 2 moles of anaminohydroxynaphthalenesulphonic acid, or more particularly 2 moles of a1-amino-8-hydroxynaphthalenesulphonic acid. An example of such dyes isthat of the formula Dye preparations, practically without water ofcomparably good quality are obtained when 15% or, preferably, 3-5 (basedon the weight of the dye) of monopropanolamine, particularly1-amino-2-hydroxy-propane, is employed. Alternatively, normalmonopropanolamine can be used.

Dyebaths, padding liquors and printing pastes are prepared with thesepreparations for the exhaustion dyeing, pad dyeing or printing oftextiles. A copper-containing disazo dye (obtained from a tetrazotiseddiaminodiphenyl and an aminohydroxynaphthalenesulphonic acid as couplingcomponent may also be selected, together with monopropanolamine, form apreparation which is primarily suitable for the exhaustion or pad dyeingor printing of cellulosic fibres such as cotton, linen and hemp.Generally, the dyes are incorporated in the preparations in the form oftheir salts, e.g. as a salt of an alkali metal. The preparations arehighly stable; after lengthy periods of storage the dyes show no sign ofdecomposition through the action of atmospheric moisture or light. Thepreparations are thus storable for long times at room temperature. 'Theyare unaffected by frost and are not subject to mould or mildewformation.

Further assistants can be incorporated in the liquid preparations ifdesired; for example dyeing assistants, such as pH stabilizers, ordispersing agents, such as alcohols or ketones, e.g. diacetone alcohol.

Dry or liquid preparations of the defined type are prepared by mixingthe afore-named components, with heating for a short time if required.They are suitable for dyeing paper, either in the stock or by dippingand coating methods, for which purpose they can be applied as truesolutions or as dispersions, previously diluted with water as required.

The advantage of the liquid preparations is case of handling. Thetroublesome dusting which occurs in weighing out powder dyes is absentwith liquids, and they are more suitable for application in continuousdyeing processes.

It is of advantage to employ dyes bearing water-solubilizing groups,e.g. carboxylic acid, sulphonic acid amide or preferably sulphonic acidgroups.

To exemplify the radicals of tetrazo compounds which can be employed forthe formation of disazo dyes of special interest for the preparations,the following diaminodiphenyl compounds may be named:

4,4'-diamino-3,3'-dihydroxy-1,1'-diphenyl,4,4'-diamino-3,3'-dimethoxy-1,1-diphenyl, 4,4'-diamino-3,3-diethoxy-1,1'-diphenyl,4,4'-diamino-3,3'-dicarboxymethoxy-1,1'-diphenyl.

Examples of suitable coupling components are those bearing activemethylene groups, e.g. acetoacetylarylamide, pyrazolones andaminopyrazoles, such as l-phenylpyrazolone-5 andl-phenyl-S-aminopyrazol; hydroxynaphthalenesulphonic acids, e.g.:

2-hydroxynaphthalene-6-sulphonic acid, 2-hydroxynaphthalene-S-sulphonicacid, 2-hydroxynaphthalene-3,6-disulphonic acid,2-hydroxynaphthalene-5,7-disulphonic acid,2-hydroxynaphthalene-6,8-disulphonic acid,Z-hydroxynaphthalene-3,6,8-trisulphonic acid,1-hydroxynaphthalene-4-sulphonic acid, l-hydroxynaphthalene-5-sulphonicacid,

SOxH

British patent specification 982,735 discloses stable dye preparationswhich contain the dye of Formula I and amino alcohols. In comparisonwith these preparations, the preparations of the present invention showsuperior heat and storage stability; the liquid preparations inparticular have notably good storage stability.

In the following examples the parts and percentages Preparation of adyebath are b wei ht and the tern eratures in de rees centi rade.

y g p g g 150 parts of softened water are run into a stainless steelEXAMPLE 1 dyebath of 200 millilitres capacity; 0.1 part of the dye Thedisazo dye of formula preparation of Example 2 and 0.5 part of Glauberssalt NH, 3u ouo NH;

soma soflNa SOaNa- SOaNa is prepared by coupling tetrazotized,4,4'-diamino-3,3'- are dissolved in the water. In this dyebath 5 partsof a dimethoxy-1,1-diphenyl with l-acetylamino-S-hydroxycotton fabricare dyed by the normal exhaustion method naphthalene-3,6-disulphonicacid, coppering the product in a fast-to-light greenish blue shade. withsimultaneous demethylation, and splitting off the Preparation of aPadding liquor acetyl groups. 109 parts of the filtercake of this dye ofapproximately 50% moisture content are washed on the 4 Parts of the lfpfeperatlon of Examples 1 and filter with a solution of 250 parts ofsodium chloride and Parts of urea are dlssolved in 400 P Of Water, and 240 parts of l-amino-2-hydroxypropane per litre of water. P P locust beang r r n In the S lution. The dye is then dried at 70-80. A sample isstored for 20 Addltfofls of 3 Parts of Y g y filthel' sulphonate 20 daysat 80 in an enclosed air atmosphere to accelerate col'ltalnmg 3 molesethylenfi OXlde groups, 3 Parts of the ageing process and thereby testits stability. The nonylphenyl P y y ether Containing 1110168chromatogram of the tested sample shows that only small ethyltme Oxide pand 5 Parts of glacial acetic acid amounts of decomposition products arepresent. On paper l w whereupon the Padding liquor is ready for P itgives a blue dyeing which is equally as bright as, and pllcatlollnotappreciably different in shade from, the dyeing Preparatwn Of a pri ti gpaste produced with a sample which has been stabilized in the 200 partsof water at 0 are run into 10 parts of the same way but not submitted tothe accelerated agelng dye preparation of Example 1, and the resultingSolution test. A sample of the nonstabilizing starting dye which has notbeen submitted to the ageing test gives a chro- 1S surfed Into 520 partsof a 30% aqueous crystal gum solution, previously mixed with 50 parts ofurea, 50

matogram showing a substantial proportion of grey departs ofthiodiethylene glycol and 60 Parts f a composition products; incomparison with the stabilized aqueous ammonium Sulphate solution.

tested sample it gives a redder and flatter blue dyeing on paper.EXAMPLE 6 EXAMPLE 2 109 parts of the dye preparation of Example 1 in theform of a 40% aqueous paste are added to 600 parts of water and stirredto form a homogeneous dispersion, whereafter 100 parts of1-amino-2-hydroxy propane are added thereto to dissolve the dye. The dyesolution is made up to 1000 parts; this dilute solution is storable forseveral months.

A dyebath can be prepared by adding 3 parts of this preparation and 2parts of anhydrous sodium carbonate to 3000 parts of softened water withstirring.

EXAMPLE 7 109 parts of the dye of Example 1 in the form of a 40% aqueouspaste are dissolved in a solution of 55 parts of1-amino-2-hydroxypropane, parts of diacetone 50 alcohol and 1000 partsof water. The dye preparation is diluted to 1400 parts and is thenstorable at room tem- 109 parts of the copper containing disazo dyedefined in Example 1 are added in the form of the moist filtercake to asolution of 105 parts of l-amino-Z-hydroxypropane, 25 parts of sodiumsulphate and 150 parts of 40 water, with continued stirring until ahomogeneous mixture is obtained. The mixture is dried in an atomizingdrier to give a preparation showing good stability similar to thatobtained by the procedure of Example 1.

EXAMPLE 3 45 109 parts of the dried and pulverized starting dye ofExample 1, 5.45 parts of l-amino-Z-hydroxypropane and 30 parts of sodiumsulphate are homogeneously mixed in a mixer. The preparation thusobtained has a storage stability comparable to that of the preparationof Example EXAMPLE 4 perature for several months.

109 parts of the copper containing disazo dye of Ex- EXAMPLE 8 ample 1in the form of a moist filtercake and 3 parts of 109 pal-ts f the dye fExample 1 in the f f a 1-amino- 2-hydroxypropane are homogeneotlsly Im1h 40% aqueous paste are dissolved in a solution of 210 a kneadlflgmachlne and the f f' drled- The dye parts of l-amino-Z-hydroxypropaneand 400 parts of Preparation u Obtained Shows slmllarly 8 Storage water.This dye preparation is storable at room tem- Stability as that P p bythe Procedure of Example pearture for several months. In place ofl-amino-Z-hy- EXAMPLE 5 droxypropane, normal monopropanolamine can beem- 109 parts of the starting dye of Example 1 in the P YFfL w i h givesa preparation of similarly good form of the moist filtercake aresuspended in a solution of stahlhty- 250 parts of sodium chloride and 40parts of l-amino-Z- MPLE 9 Y I YI P P litre 9 q Attel: filtelfing and100 parts of chemically bleached sulphite cellulose pulp 'y a y p p 1SOhtalned Whlch Wlthstands 65 in water are refined in a heater, 1 part ofthe dye preparah accelerated ageing test q y as Well as the prepara tionof Example 6 is added, and after 15 minutes the paper tion of Example I-stock is sized and fixed. Paper made from this stock is dyed Dyeing6x31111316 in a greenish blue shade of medium depth which has good Acharge of parts of chemically bleached sulphite fastness properties. Thebackwater from the papermaking cellulose pulp and 30 parts of chemicallybleached sul- 70 machine is colourless.

phate cellulose pulp in 200 parts of water is beaten in a pulper to thedesired degree of fineness. At this point EXAMPLE 10 0.05 part of thedye preparation of Example 2 are strewn A dyebath is prepared with 3000parts of softened in, and after 20 minutes the stock in converted intoan water, 2 parts of anhydrous sodium carbonate and 3 parts absorbentpaper dyed in a pale blue shade. of the dye preparation of Example 7. At30 parts of a wet-out cotton fabric are entered into the bath, afterwhich parts of sodium sulphate are added. The bath is raised to 100 inminutes, with two further additions of 10 parts of sodium sulphate atand After dyeing for 15 minutes at a final 10 parts of sodium sulphateare added and the bath is then allowed to cool. At 50 the dyed cotton isremoved from the bath, rinsed well with cold water and dried at 60. Thegreenish blue dyeing obtained is fast to light and wet treatments.

The dye used for the dye preparations referred to in the precedingexamples can be replaced by the dyes of Formulae II, III or IV below,with which preparations of similarly good quality are obtained.

6 7. A stable concentrated dye preparation according to claim 6containing one copperized disazo dye bearing the radical of atetrazotized 4,4'-diamino-3,3'-dialkoxy-1,1- diphenyl and 2 moles of aI-amino-S-hydroxynaphthalene- 5 sulphonic acid as coupling component.

8. A liquid preparation according to claim 7 with 1 part by weight ofcopperized water-soluble disazo dye bearing the radical of atetrazotized 4,4'-diamino-3,3'-dialkoxy-1, l'-diphenyl and 2 moles of a1-amino-8-hydroxynaphthalene-sulphonic acid as coupling component, 2 to15 parts by weight of water and 0.5 to 5 parts by weight ofmonopropanolamine.

9. Dye preparation according to claim 6 wherein the to 15 parts byweight of water per part by weight of dye. 5. Dye preparation accordingto claim 1 wherein the metallized dye is copperized dye.

6. Dye preparation according to claim 5 wherein the disazo dye bears theradical of a tetrazotized diaminodiphenyl.

tetrazotized diaminodiphenyl is coupled with 2 moles ofl-amino-8-hydroxynaphthalene-sulphonic acid.

10. Dye preparation according to claim 1 wherein the azo dye bears theradical of tetrazotized 4,4'-diamino-3,3'- dialkoXy-1,l-diphenyl.

11. Liquid dye preparation according to claim 1 wherein the metallizeddye is water-soluble and which contains 5 to 15 parts by weight of waterand 0.5 to 2 parts by weight of monopropanolamine per part by weight ofdye.

12. Dye preparations according to claim 1 wherein the dye is dye of theformula E0 -soan 13. Dye preparation according to claim 1 wherein thedye is dye of the formula HzN OCu (I) (I) Cu-O NH;

14. Dye preparations according to claim 1 wherein the dye is dye of theformula 15. Dye preparations according to claim 1 wherein the dye is dyeof the formula HzN O-( 3u (I) (I) In-0 N| Hl OaNa OzNa References CitedUNITED STATES PATENTS 2,842,536 7/1958 Bauer et a1. 260148 FOREIGNPATENTS 982,735 2/1965 Great Britain 260148 LEWIS GOTTS, PrimaryExaminer D. M. PAPUGA, Assistant Examiner US. Cl. X.R. 2601-61

